Nanocrystal electroluminescence device and fabrication method thereof

ABSTRACT

A nanocrystal electroluminescence device comprising a polymer hole transport layer, a nanocrystal light-emitting layer and an organic electron transport layer wherein the nanocrystal light-emitting layer is independently and separately formed between the polymer hole transport layer and the organic electron transport layer. According to the nanocrystal electroluminescence device, since the hole transport layer, the nanocrystal light-emitting layer and the electron transport layer are completely separated from one another, the electroluminescence device provides a pure nanocrystal luminescence spectrum having limited luminescence from other organic layers and substantially no influence by operational conditions, such as voltage. Further, a method for fabricating the nanocrystal electroluminescence device.

BACKGROUND OF THE INVENTION

This non-provisional application claims priority under 35 U.S.C. 119(a)on Korean Patent Application No. 42200 filed on Jun. 9, 2004 which isherein expressly incorporated by reference.

1. Field of the Invention

The present invention relates to an electroluminescence device, and amethod for fabricating the electroluminescence device. Moreparticularly, the present invention relates to a nanocrystalelectroluminescence device comprising a polymer hole transport layer, ananocrystal light-emitting layer and an organic electron transport layerwherein the nanocrystal light-emitting layer is independently andseparately formed between the polymer hole transport layer and theorganic electron transport layer, and a method for fabricating thenanocrystal electroluminescence device.

2. Description of the Related Art

A nanocrystal is defined as a material having a crystal structure at thenanometer-scale level, and consists of a few hundred to a few thousandatoms. Since the small-sized nanocrystal has a large surface area perunit volume, most of the atoms constituting the nanocrystal are presentat the surface of the nanocrystal. Based on this structure, thenanocrystal exhibits quantum confinement effects, and shows electrical,magnetic, optical, chemical and mechanical properties different fromthose inherent to the constituent atoms of the nanocrystal. That is, thecontrol over the physical size of the nanocrystal enables the control ofvarious properties.

Vapor deposition processes, such as metal organic chemical deposition(MOCVD) and molecular beam epitaxy (MBE), have been conventionally usedto prepare nanocrystals. On the other hand, a wet chemistry techniquewherein a precursor material is added to an organic solvent to grownanocrystals to a desired size has made remarkable progress in the pastdecade. According to the wet chemistry technique, as the crystals aregrown, the organic solvent is naturally coordinated to the surface ofthe quantum dot crystals and acts as a dispersant. Accordingly, theorganic solvent allows the crystals to grow to the nanometer-scalelevel. The wet chemistry technique has an advantage in that nanocrystalscan be uniformly prepared in size and shape in a relatively simplemanner at low cost, compared to conventional vapor deposition processes,e.g., MOCVD and MBE.

However, since nanocrystals prepared by the wet chemistry technique arecommonly separated and are then dispersed in an organic solvent,techniques for forming a thin film of the nanocrystals in a solid stateare required in order to apply the nanocrystals to electroluminescencedevices.

In nanocrystal electroluminescence devices reported hitherto, thenanocrystals are used as luminescent materials, or have functions oflight emission, in combination with charge transport. The firstelectroluminescence device employing nanocrystals was suggested in U.S.Pat. No. 5,537,000. The electroluminescence device is formed using oneor more layers of nanocrystals as an electron transport layer, andpreferably capable of emitting light. Accordingly, the luminescencewavelengths of the electroluminescence device are varied in response tothe changes in the voltages applied to the device.

PCT publication WO/03/084292 teaches a device wherein a layer of anorganic-inorganic hybrid matrix containing nanocrystals is disposedbetween two electrodes. Specifically, the device is fabricated by mixingnanocrystals and a low molecular weight hole transporting material, suchas N,N-diphenyl-N,N-bis(3-methylphenyl)-(1,1-biphenyl)-4,4-diamine(TPD), with a solvent, and spin coating the mixture on an electrode.When the coating conditions and the mixing ratio between thenanocrystals and the hole transporting material are appropriatelycontrolled, a nanocrystal layer is formed on top of a hole transportlayer due to the difference in the intermolecular force or densitybetween the nanocrystals and the hole transporting material. However,although the nanocrystal layer is formed on top of the hole transportlayer, the hole transporting material is mixed with the nanocrystals inthe transport layer. Accordingly, the overlying electron transport layeris in contact with the hole transport layer, and thus the hole andelectron transport layers as well as the nanocrystal layer emit light.To solve this problem, the PCT publication discloses a technique forarranging a hole blocking layer on a thin film of the hole transportlayer containing the nanocrystals, followed by forming the electrontransport layer on the hole blocking layer. Meanwhile, the holetransporting material mixed with the nanocrystals has a low molecularweight. If a polymer is used as the hole transporting material, itssolubility is low and thus the polymer is limited to material which canbe dissolved in solvents which dissolve the nanocrystal. Although thepolymer which can be dissolved are used, the solubility of the polymeris not sufficiently high, rendering it difficult to control thethickness of the nanocrystal layer and the hole transport layer.

U.S. Pat. No. 6,049,090 describes a device wherein a mixed layer ofnanocrystals and a matrix as a light-emitting layer is disposed betweentwo electrodes. According to the device, the matrix is selected to havea wider bandgap energy, a higher conduction band energy level and alower valence band energy level than the nanocrystals so as to allow thenanocrystals to emit light well and trap electrons and holes innanocrystals, thereby enhancing the luminescence efficiency of thedevice.

As stated above, the conventional electroluminescence devices employingnanocrystals as luminescent materials are devices wherein thenanocrystals have functions of light emission in combination with chargetransport, are mixed with a hole transporting material to form a mixedlayer, or are mixed with a hole transporting material and coated to forma nanocrystal layer separately formed on a hole transport layer due tothe density difference depending on the processing conditions. However,since none of these conventional electroluminescence devices provide apure nanocrystal luminescence spectrum, they have a problem of low colorpurity.

OBJECTS AND SUMMARY

Therefore, the present invention has been made in view of the aboveproblems of the related art, and it is an object of the presentinvention to provide an electroluminescence device comprising a polymerhole transport layer, a nanocrystal light-emitting layer and an organicelectron transport layer wherein the nanocrystal light-emitting layer isindependently and separately formed between the polymer hole transportlayer and the organic electron transport layer, thereby providing a purenanocrystal luminescence spectrum and increasing the color purity of theelectroluminescence device.

It is another object of the present invention to provide a method forfabricating the electroluminescence device wherein materials for a holetransport layer can be selected, regardless of the solubility in asolvent which disperses nanocrystals.

In accordance with one aspect of the present invention, the aboveobjects can be accomplished by an electroluminescence device comprisinga polymer hole transport layer, a nanocrystal light-emitting layer andan organic electron transport layer wherein the nanocrystallight-emitting layer in contact with the polymer hole transport layer isseparately formed between the polymer hole transport layer and theorganic electron transport layer.

In accordance with another aspect of the present invention, there isprovided a method for fabricating the electroluminescence device,comprising the steps of: patterning a hole-injecting anode on asubstrate and forming a polymer hole transport layer thereon; coating ananocrystal dispersion on the polymer hole transport layer to form ananocrystal light-emitting layer; forming an organic electron transportlayer on the nanocrystal light-emitting layer; and forming anelectron-injecting cathode on the organic electron transport layer.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other objects, features and other advantages of thepresent invention will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings, in which:

FIG. 1 is a cross-sectional view schematically showing a nanocrystalelectroluminescence device according to one embodiment of the presentinvention;

FIG. 2 shows cross-sectional views illustrating the steps of a methodfor fabricating a nanocrystal electroluminescence device according toone embodiment of the present invention;

FIG. 3 a is a partial cross-sectional view schematically showing aconventional electroluminescence device in which after a mixture ofnanocrystals and a hole transporting material is coated, the resultinghole transport layer and nanocrystal layer are incompletely separatedfrom each other; FIG. 3 b is a partial cross-sectional view showinganother conventional electroluminescence device in which after a mixtureof nanocrystals and a hole transporting material is coated, thenanocrystals are uniformly dispersed in the hole transporting materialto form one mixed layer; and FIG. 3 c is a partial cross-sectional viewschematically showing a nanocrystal electroluminescence device of thepresent invention in which after a hole transporting material is coatedto form a thin film, baked, and coated with nanocrystals, a nanocrystallight-emitting layer is completely separated from a hole transportlayer;

FIG. 4 is a photoluminescence spectrum of silica nanocrystalssurface-bound by a photosensitive compound, which is prepared inPreparative Example 1 of the present invention;

FIG. 5 is a photoluminescence spectrum of silica nanocrystalssurface-bound by a photosensitive compound, which is prepared inPreparative Example 2 of the present invention;

FIGS. 6 a and 6 b are luminescence spectra of electroluminescencedevices fabricated in Examples 1 and 2 of the present inventionaccording to the changes in the voltages applied to the devices,respectively;

FIG. 7 shows luminescence spectra of an electroluminescence devicefabricated in Example 3 of the present invention according to thechanges in the voltages applied to the device; and

FIG. 8 shows luminescence spectra of a conventional electroluminescencedevice fabricated in Comparative Example 1 according to the changes inthe voltages applied to the device.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will now be described in more detail withreference to the accompanying drawings.

An electroluminescence device according to the present inventioncomprises a polymer hole transport layer, a nanocrystal light-emiftinglayer and an organic electron transport layer wherein the nanocrystallight-emitting layer in contact with the polymer hole transport layer isseparately and independently formed between the polymer hole transportlayer and the organic electron transport layer.

FIG. 1 is a cross-sectional view schematically showing the nanocrystalelectroluminescence device according to one embodiment of the presentinvention. Referring to FIG. 1, the electroluminescence device of thepresent invention comprises an anode 20, a polymer hole transport layer30, a nanocrystal light-emitting layer 40, an organic electron transportlayer 50, and a cathode 60 layered in this order on a transparentsubstrate 10. The polymer hole transport layer 30 is formed of amaterial capable of transporting holes, and the electron transport layer50 is made of a material capable of transporting electrons. When avoltage is applied between the two electrodes, the anode 20 injectsholes into the hole transport layer 30, and the cathode 60 injectselectrons into the electron transport layer 50. The injected holes arecombined with the injected electrons at the same molecules to formexciton pairs, and then the exciton pairs are recombined to emit light.

Optionally, the electroluminescence device of the present inventionfurther comprises a hole injection layer interposed between the anode 20and the hole transport layer 30; an electron blocking layer, a holeblocking layer or an electron/hole blocking layer interposed between thehole transport layer 30 and the nanocrystal light-emitting layer 40; oran electron blocking layer, a hole blocking layer or an electron/holeblocking layer interposed between the nanocrystal light-emitting layer40 and the electron transport layer 50.

The transparent substrate 10 used in the electroluminescence device ofthe present invention may be a substrate used in common organicelectroluminescence devices. A glass or transparent plastic substrate ispreferred in terms of superior transparency, superior surfacesmoothness, ease of handling, and excellent waterproofness. Specificexamples of the transparent substrate include polyethyleneterephthalate,polycarbonate substrates, and the like. The thickness of the transparentsubstrate 10 is preferably in the range of 0.3˜1.1 mm.

The anode 20 formed on the transparent substrate 10 may be made of anelectrically conductive metal or its oxide so that it can easily injectsholes. As specific examples, indium tin oxide (ITO), indium zinc oxide(IZO), nickel (Ni), platinum (Pt), gold (Au), silver (Ag), and iridium(Ir) may be mentioned.

Examples of materials for the hole transport layer 30 include, but arenot limited to, poly(3,4-ethylenedioxythiophene) (PEDOT)/polystyrenepara-sulfonate (PSS), poly-N-vinylcarbazole derivatives,polyphenylenevinylene derivatives, polyparaphenylene derivatives,polymethacrylate derivatives, poly(9,9-octylfluorene) derivatives,poly(spiro-fluorene) derivatives, and the like. The thickness of thehole transport layer 30 is preferably in the range of 10 nm to 100 nm.

Materials commonly used in the art can be used to form the organicelectron transport layer 50. Specific examples of materials for theorganic electron transport layer 50 include, but are not limited to,oxazoles, isooxazoles, triazoles, isothiazoles, oxydiazoles,thiadiazoles, perylenes, and aluminum complexes, includingtris(8-hydroxyquinoline)-aluminum (Alq3), Balq, Salq and Almq3. Thethickness of the organic electron transport layer 50 is preferablybetween 10 nm and 100 nm.

Suitable materials for the electron blocking layer, the hole blockinglayer or the electron/hole blocking layer are those commonly used in theart. Specific examples include, but are not limited to,3-phenyl-4-(1-naphthyl)-5-phenyl-1,2,4-triazole (TAZ),2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP), phenanthrolines,imidazoles, triazoles, oxadiazoles, and aluminum complexes. Thethickness of the electron blocking layer, hole blocking layer andelectron/hole blocking layer is preferably in the range of 5 nm to 50nm.

Examples of materials for the electron-injecting cathode 60 include, butare not limited to, metals having a sufficiently low work function toeasily inject electrons, such as [I], Ca, Ba, Ca/Al, LiF/Ca, LiF/Al,BaF₂/Al, BaF₂/Ca/Al, Al, Mg, and Ag:Mg alloys. The thickness of thecathode is preferably in the range of 50 nm to 300 nm.

Nanocrystals that can be used in the present invention include most ofthe nanocrystals prepared by a wet chemistry technique, such as metalnanocrystals and semiconductor nanocrystals. Specifically, thenanocrystal light-emitting layer 40 is made of at least one materialselected from the group consisting of metal nanocrystals, such as Au,Ag, Pt, Pd, Co, Cu and Mo, Group II-VI compound semiconductornanocrystals, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe andHgTe, and Group III-V compound semiconductor nanocrystals, such as GaN,GaP, GaAs, InP and InAs, and PnS, PbSe, PbTe. If the nanocrystallight-emitting layer is made of a mixture of two or more nanocrystals,the nanocrystals may exist in the state of a simple mixture, fusedcrystals in which the nanocrystals are partially present in the samecrystal structure, or an alloy. The thickness of the nanocrystallight-emitting layer is between 3 nm and 30 nm.

The present invention is directed to a method for fabricating thenanocrystal electroluminescence device. According to the method of thepresent invention, a polymer hole transporting material is coated on ahole-injecting anode by various coating processes, and baked to form arigid thin film of a polymer hole transport layer. A nanocrystaldispersion is coated on the polymer hole transport layer by variouscoating processes to form a thin film of a nanocrystal light-emittinglayer. At this time, the nanocrystal dispersion is prepared bydispersing nanocrystals in a solvent which does not dissolve the polymerhole transport layer. The nanocrystal light-emitting layer thus formedis separated from the polymer hole transport layer. Thereafter, anorganic electron transport layer and an electron-injecting cathode aresequentially formed on the nanocrystal light-emitting layer.

FIG. 2 shows cross-sectional views illustrating the steps of the methodfor fabricating the electroluminescence device shown in FIG. 1, inaccordance with the present invention. Referring to FIG. 2, ahole-injecting anode 20 is patterned on a substrate 10, and then apolymer hole transporting material is coated on the substrate 10 byvarious coating processes, such as spin coating, to form a polymer holetransport layer 30. The polymer hole transport layer 30 is then bakedinto a rigid thin film so that the polymer hole transport layer is notdamaged in the subsequent formation step of a nanocrystal light-emittinglayer. Next, a nanocrystal dispersion is coated on the polymer holetransport layer 30 by various coating processes, such as spin coating,to form a nanocrystal light-emitting layer 4. At this time, thenanocrystal dispersion is prepared by dispersing nanocrystals in asolvent which does not substantially dissolve the polymer hole transportlayer 30. Thereafter, an organic electron transport layer 50 is formedon the nanocrystal light-emitting layer 40, and then a cathode is formedthereon to form the final electroluminescence device.

The substrate 10 on which the anode 20 is patterned is commonly washedwith solvents, such as a neutral detergent, deionized water, acetone andisopropyl alcohol, and is then subjected to UV-ozone and plasmatreatment.

According to the method of the present invention, the nanocrystallight-emitting layer is formed in accordance with the followingprocedure. Nanocrystals surface-bound by a photosensitive compound aredispersed in a solvent which does not damage the polymer hole transportlayer to obtain a nanocrystal dispersion. The nanocrystal dispersion iscoated on the polymer hole transport layer to form a thin film of thenanocrystals. Altematively, nanocrystals surface-bound by a materialcontaining no photosensitive functional group and a photosensitivecompound are dispersed in a solvent which does not damage the polymerhole transport layer to obtain a nanocrystal dispersion. The nanocrystaldispersion is coated on the polymer hole transport layer to form a thinfilm of the nanocrystals.

The solvent which does not damage the hole transport layer and candisperse the nanocrystals is selected from the group consisting ofwater, pyridine, ethanol, propanol, butanol, pentanol, hexanol, toluene,chloroform, chlorobenzene, THF, cyclohexane, cyclohexene, methylenechloride, pentane, hexane, heptane, octane, nonane, decane, undecane,dodecane, and mixtures thereof.

Prior to coating the organic electron transporting material on thenanocrystal light-emitting layer 40, the nanocrystal light-emittinglayer 40 can be exposed to UV light at a wavelength of 200 nm to 450 nmto crosslink it. The luminescence wavelength of the nanocrystallight-emitting layer 40 is in the range of 350 nm to 1,300 nm.

The solvent which does not damage the nanocrystal light-emitting layer,the polymer hole transporting material, and the hole transport layer,and can disperse the nanocrystals is as described above. Theconcentration of the nanocrystal dispersion is preferably between 0.01wt % and 10 wt %, more preferably between 0.1 wt % and 5 wt %, and mostpreferably between 0.2 wt % and 2 wt %.

As the material for the organic electron transport layer 50, a low- orhigh-molecular weight material can be used. Vacuum deposition and wetcoating can be employed as the coating processes. The first process forforming the organic electron transport layer 50 by wet coating isperformed by the following procedure. Nanocrystals surface-bound by aphotosensitive compound are formed into a thin film of the nanocrystals,and exposed to UV light to crosslink the thin film, thereby making thethin film insoluble in a solvent containing an electron transportingmaterial. Thereafter, the organic electron transporting material iswet-coated on the nanocrystal layer to form the organic electrontransport layer 50. The second process for forming the organic electrontransport layer 50 by wet coating is performed by the followingprocedure. Nanocrystals surface-bound by a material containing nophotosensitive functional group, and a photosensitive compound arethoroughly mixed, formed into a thin film of the nanocrystals, andexposed to UV light to crosslink the photosensitive material, therebyforming a network structure. The network structure traps thenanocrystals, which makes the thin film insoluble in a solventcontaining an electron transporting material. Thereafter, the organicelectron transporting material is wet-coated on the nanocrystal layer toform the organic electron transport layer 50.

The organic material surface-bound to the nanocrystals contains at leastone functional group selected from the group consisting of acetyl,acetic acid, phosphine, phosphonic acid, alcohol, vinyl, carboxyl,amide, phenyl, amine, acryl, silane, cyano and thiol groups at one orboth terminals of its alkyl chain or aromatic moiety.

The photosensitive compound surface-bound to the nanocrystals contains adouble bond, a carboxyl group, an amide group, a phenyl group, abiphenyl group, a peroxide group, an amine group, an acryl group, or thelike.

The method for fabricating the electroluminescence device according tothe present invention may further comprise the step of inserting a holeinjection layer between the anode and the hole transport layer;inserting an electron blocking layer between the light-emitting layerand the hole transport layer; or inserting a hole blocking layer betweenthe nanocrystal light-emitting layer and the electron transport layer.

FIGS. 3 a and 3 b show states wherein a mixture of nanocrystals and aorganic hole transporting material is coated by spin coating to formthin films. The organic hole transporting material used herein may be alow- or high-molecular weight material. FIG. 3 a shows a state whereinafter a mixture of nanocrystals and a organic hole transporting materialis spin-coated, a nanocrystal layer is formed on top of a hole transportlayer due to the difference in the intermolecular force or densitybetween the nanocrystals and the hole transporting material. However,although the nanocrystals 25 can form a layer partially separated fromthe hole transporting material, most of the hole transporting materialis mixed with the nanocrystals in the nanocrystal layer. FIG. 3 b showsa state wherein nanocrystals 25 are uniformly dispersed in a holetransporting material to form one mixed layer. FIG. 3 c shows a statewherein a nanocrystal light-emitting layer 40 is completely separatedfrom a hole transport layer 30 by the method of the present inventionshown in FIG. 2.

The fabrication of the electroluminescence device of the presentinvention does not require particular fabrication apparatuses andmethods, in addition to the formation of the independent and separatenanocrystal light-emitting layer. The electroluminescence device of thepresent invention can be fabricated in accordance with conventionalfabrication methods using common luminescent materials.

To form the hole transport layer 30 and the electron transport layer 50into thin films, spin coating, dip coating, spray coating, bladecoating, and other coating processes can be used. The exposure of thethin films used in the method of the present invention may be carriedout by a contact exposure or non-contact exposure process. The electrontransport layer 50 can be formed on the nanocrystal light-emitting layer40 by thermal deposition, molecular deposition or chemical deposition.

After formation of the thin films, drying can be carried out at 20°C.˜300° C. and preferably 40° C.˜120° C. In addition, the energy forphotosensitization treatment is dependent on the thickness of the thinfilms, and is preferably between 50 mJ/cM² and 850 mJ/cm². When theexposure energy is out of this range, sufficient crosslinking is notlikely to take place, or there is a risk of damage to the thin film.Light sources usable for the light exposure preferably have an energy inthe range of about 100 W to about 800 W at an effective wavelength of200˜500 nm and preferably 300˜400 nm.

Hereinafter, the present invention will be explained in more detail withreference to the following examples. However, these examples are madeonly for illustrative purposes of preferred embodiments and are not tobe construed as limiting the scope of the invention.

PREPARATIVE EXAMPLE 1. Preparation of CdSeS Nanocrystals

16 g of trioctyl amine (hereinafter, referred to as ‘TOA’), 0.5 g ofoleic acid, and 0.4 mmol of cadmium oxide were charged into a 125 mlflask equipped with a reflux condenser. The reaction temperature of themixture was adjusted to 300° C. with stirring. Separately, a selenium(Se) powder was dissolved in trioctyl phosphine (hereinafter, referredto as TOP) to obtain an Se-TOP complex solution (Se concentration: about0.25 M), and a sulfur (S) powder was dissolved in TOP to obtain an S-TOPcomplex solution (S concentration: about 1.0 M). 0.9 ml of the S-TOPcomplex solution and 0.1 ml of the Se-TOP complex solution were rapidlyfed to the previous mixture, and then reacted for 4 minutes withstirring. After the reaction was completed, the reaction mixture wascooled to room temperature as rapidly as possible. Ethanol as anon-solvent was added to the reaction mixture, and the resulting mixturewas then centrifuged. After the obtained precipitates were separatedfrom the mixture by decanting the supematant, 1 wt % of the precipitateswere dispersed in toluene to prepare a dispersion of CdSeS nanocrystals.The nanocrystals emitted light green light under a UV lamp at 365 nm.FIG. 4 shows a photoluminescence spectrum of the dispersion of CdSeSnanocrystals. As shown in FIG. 4, a photoluminescence peak having afull-width at half maximum (FWHM) of about 30 nm was observed around 552nm.

PREPARATIVE EXAMPLE 2. Preparation of CdSe/ZnS Nanocrystals

16 g of TOA, 0.5 g of oleic acid, and 0.1 mmol of cadmium oxide weresimultaneously charged into a 125 ml flask equipped with a refluxcondenser. The reaction temperature of the mixture was adjusted to 300°C. with stirring. Separately, a Se powder was dissolved in TOP to obtainan Se-TOP complex solution (Se concentration: about 2 M). 1 ml of theS-TOP complex solution was rapidly fed to the previous mixture, and thenreacted for about 10 seconds with stirring. After the reaction wascompleted, the reaction mixture was cooled to room temperature asrapidly as possible. Ethanol as a non-solvent was added to the reactionmixture, and the resulting mixture was then centrifuged. After theobtained precipitates were separated from the mixture by decanting thesupematant, the precipitates were dispersed in toluene to prepare adispersion of CdSe nanocrystals.

On the other hand, 8 g of TOA and 0.4 mmol of zinc acetate weresimultaneously charged into a 125 ml flask equipped with a refluxcondenser. The reaction temperature of the mixture was adjusted to 260°C. with stirring. After the dispersion of CdSe nanocrystals was added tothe reaction mixture, the reaction was allowed to proceed for about 1hour while an S-TOP complex solution was slowly added thereto. Aftercompletion of the reaction, the reaction mixture was cooled to roomtemperature as rapidly as possible. Ethanol as a non-solvent was addedto the reaction mixture, and the resulting mixture was then centrifuged.After the obtained precipitates were separated from the mixture bydecanting the supernatant, the precipitates were dispersed in toluene toprepare a dispersion of CdSe/ZnS nanocrystals. The nanocrystals emittedlight green light under a UV lamp at 365 nm. FIG. 5 shows aphotoluminescence spectrum of the dispersion of CdSe/ZnS nanocrystals.As shown in FIG. 5, a photoluminescence peak having a full-width at halfmaximum (FWHM) of about 30 nm was observed around 527 nm.

EXAMPLE 1. Fabrication of Electroluminescence Device Employing CdSeSNanocrystal Light-emitting Layer Dispersed in Octane

This example shows the fabrication of an electroluminescence devicewherein a nanocrystal light-emitting layer is independently andseparately formed. First, an ITO-patterned glass substrate wassequentially washed with a neutral detergent, deionized water, water andisopropyl alcohol, and was then subjected to UV-ozone treatment. Asolution of 1 wt % ofpoly(9,9′-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB) inchlorobenzene was spin-coated on the ITO-patterned substrate to athickness of about 50 nm, and then baked at 180° C. for 10 minutes toform a hole transport layer. A dispersion of the CdSeS nanocrystals (1wt %) prepared in Preparative Example 1 in octane was spin-coated on thehole transport layer, and dried to form a nanocrystal light-emittinglayer having a thickness of about 5 nm. At this time, the octane usedherein is a solvent which does not dissolve the hole transport layer.

(3-4-Biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) wasdeposited on the completely dried nanocrystal light-emitting layer toform a hole blocking layer having a thickness of 10 nm, and thentris(8-hydroxyquinoline)-aluminum (Alq3) was deposited thereon to forman electron transport layer having a thickness of about 30 nm. LiF andaluminum were sequentially deposited on the electron transport layer tothicknesses of 1 nm and 200 nm, respectively, to form a cathode, therebyfabricating the final electroluminescence device.

FIG. 6 a shows luminescence spectra of the electroluminescence deviceaccording to the changes in the voltages applied to the device. As shownin FIG. 6 a, a luminescence peak having a full-width at half maximum(FWHM) of about 40 nm was observed around 556 nm.

EXAMPLE 2. Fabrication of Electroluminescence Device Employing CdSeSNanocrystal Light-emitting Layer Dispersed in Chlorobenzene

First, an ITO-pattemed glass substrate was sequentially washed with aneutral detergent, deionized water, water and isopropyl alcohol, and wasthen subjected to UV-ozone treatment. A solution of 1 wt % ofpoly(9,9′-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB) inchlorobenzene was spin-coated on the ITO-patterned substrate to athickness of about 50 nm, and then baked at 180° C. for 10 minutes toform a hole transport layer. A dispersion of 1 wt % of the CdSeSnanocrystals prepared in Preparative Example 1 in chlorobenzene wasspin-coated on the hole transport layer, and dried to form a nanocrystallight-emitting layer having a thickness of about 5 nm. At this time, thechlorobenzene used herein is a solvent which does not dissolve the holetransport layer.

(3-4-Biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) wasdeposited on the completely dried nanocrystal light-emitting layer toform a hole blocking layer having a thickness of 10 nm, and thentris(8-hydroxyquinoline)-aluminum (Alq3) was deposited thereon to forman electron transport layer having a thickness of about 30 nm. LiF andaluminum were sequentially deposited on the electron transport layer tothicknesses of 1 nm and 200 nm, respectively, to form an electrode,thereby fabricating the final electroluminescence device.

FIG. 6 b shows luminescence spectra of the electroluminescence devicewherein the nanocrystal light-emitting layer was independently andseparately formed, according to the changes in the voltages applied tothe device. As shown in FIG. 6 b, a luminescence peak having afull-width at half maximum (FWHM) of about 50 nm was observed around 556nm.

EXAMPLE 3. Fabrication of Electroluminescence Device Employing CdSe/ZnSNanocrystal Light-emitting Layer Dispersed in Octane and Including NoHole Blocking Layer

First, an ITO-pattemed glass substrate was sequentially washed with aneutral detergent, deionized water, water and isopropyl alcohol, and wasthen subjected to UV-ozone treatment. A solution of 1 wt % ofpoly(9,9′-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB) inchlorobenzene was spin-coated on the ITO-patterned substrate to athickness of about 50 nm, and then baked at 180° C. for 10 minutes toform a hole transport layer. A dispersion of the CdSe/ZnS nanocrystals(1 wt %) prepared in Preparative Example 2 in octane was spin-coated onthe hole transport layer, and dried to form a nanocrystal light-emittinglayer having a thickness of about 5 nm. At this time, the octane usedherein is a solvent which does not dissolve the hole transport layer.

Tris(8-hydroxyquinoline)-aluminum (Alq3) was deposited on the completelydried nanocrystal light-emitting layer to form an electron transportlayer having a thickness of about 40 nm. LiF and aluminum weresequentially deposited on the electron transport layer to thicknesses of1 nm and 200 nm, respectively, to form an electrode, thereby fabricatingthe final electroluminescence device.

FIG. 7 shows luminescence spectra of the electroluminescence devicewherein the nanocrystal light-emifting layer was independently andseparately formed, according to the changes in the voltages applied tothe device. As shown in FIG. 7, a luminescence peak having a full-widthat half maximum (FWHM) of about 46 nm was observed around 530 nm.

COMPARATIVE EXAMPLE 1. Fabrication of Conventional ElectroluminescenceDevice from Mixed Solution of Hole Transporting Material and CdSeSNanocrystals

This comparative example realizes a method for fabricating aconventional electroluminescence device wherein after a mixture ofnanocrystals and a hole transporting material is coated, the resultinghole transport layer and nanocrystal layer are separated from each otherdue to the difference in the density of the nanocrystals, which resultsfrom phase separation arising during the coating.

First, an ITO-pattemed glass substrate was sequentially washed with aneutral detergent, deionized water, water and isopropyl alcohol, and wasthen subjected to UV-ozone treatment. A solution of 1 wt % ofpoly(9,9′-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB) andthe CdSeS nanocrystals prepared in Preparative Example 1 inchlorobenzene was spin-coated on the ITO-patterned substrate, and thenbaked at 180° C. for 10 minutes to form a hole transport layer in whicha nanocrystal light-emifting layer was included. At this time, theweight ratio of the TFB to the CdSeS nanocrystals was adjusted to 1:1.

(3-4-Biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) wasdeposited on the completely dried hole transport layer to form a holeblocking layer having a thickness of 10 nm, and thentris(8-hydroxyquinoline)-aluminum (Alq3) was deposited thereon to forman electron transport layer having a thickness of about 30 nm. LiF andaluminum were sequentially deposited on the electron transport layer tothicknesses of 1 nm and 200 nm, respectively, to form an electrode,thereby fabricating the final electroluminescence device.

FIG. 8 shows luminescence spectra of the electroluminescence deviceaccording to the changes in the voltages applied to the device. It wasconfirmed from FIG. 8 that the hole transport layer including thenanocrystal layer, as well as the electron transport layers emittedlight.

As apparent from the foregoing, the electroluminescence device of thepresent invention has a direct transition-type bandgap ranging from thevisible to the infrared range, and includes a nanocrystal light-emittinglayer which is made of nanocrystals with enhanced luminescenceefficiency and is independently and separately formed. Accordingly, theelectroluminescence device of the present invention provides a purenanocrystal luminescence spectrum having limited luminescence from otherorganic layers and substantially no influence by operational conditions,such as voltage, resulting in a high color purity. In addition,according to the method of the present invention, materials for a holetransport layer can be selected, regardless of the solubility in asolvent which disperses nanocrystals. Accordingly, the method of thepresent invention has an advantage in terms of improved workability.

Although the preferred embodiments of the present invention have beendisclosed for illustrative purposes, those skilled in the art willappreciate that various modifications, additions and substitutions arepossible, without departing from the scope and spirit of the inventionas disclosed in the accompanying claims.

1. An electroluminescence device comprising a polymer hole transportlayer, a nanocrystal light-emitting layer and an organic electrontransport layer, wherein the nanocrystal light-emitting layer in contactwith the polymer hole transport layer is independently formed betweenthe polymer hole transport layer and the organic electron transportlayer.
 2. The electroluminescence device according to claim 1, whereinthe electroluminescence device has a structure consisting of an anode, apolymer hole transport layer, a nanocrystal light-emitting layer, anorganic electron transport layer, and a cathode layered in this order ona transparent substrate.
 3. The electroluminescence device according toclaim 2, further comprising a hole injection layer, an electron blockinglayer, a hole blocking layer or an electron/hole blocking layerinterposed between the polymer hole transport layer and the anode, orbetween the organic electron transport layer and the nanocrystallight-emitting layer.
 4. The electroluminescence device according toclaim 1, wherein the nanocrystal light-emitting layer is made of atleast one material selected from the group consisting of metalnanocrystals, Group II-VI compound semiconductor nanocrystals, and GroupIII-V compound semiconductor nanocrystals and PbS, PbSe and PbTe,wherein the metal nanocrystals include Au, Ag, Pt, Pd, Co, Cu and Mo,the Group II-IV compound semiconductor nanocrystals include CdS, CdSe,CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe and HgTe, the Group III-V compoundsemiconductor nanocrystals include GaN, GaP, GaAs, InP and InAs; andwhen the nanocrystal light-emitting layer is made of a mixture of two ormore nanocrystals, the nanocrystals exist in the state of a simplemixture, fused crystals in which the nanocrystals are partially presentin the same crystal structure, or an alloy.
 5. The electroluminescencedevice according to claim 1, wherein the polymer hole transport layer ismade of a material selected from the group consisting ofpoly(3,4-ethylenedioxythiophene) (PEDOT)/polystyrene para-sulfonate(PSS), poly-N-vinylcarbazole derivatives, polyphenylenevinylenederivatives, polyparaphenylene derivatives, polymethacrylatederivatives, poly(9,9-octylfluorene) derivatives, andpoly(spiro-fluorene) derivatives.
 6. The electroluminescence deviceaccording to claim 1, wherein the nanocrystal light-emitting layer has athickness of 3 nm˜30 nm.
 7. The electroluminescence device according toclaim 1, wherein the electron transport layer is made of a materialselected from the group consisting of oxazoles, isooxazoles, triazoles,isothiazoles, oxydiazoles, thiadiazoles, perylenes,tris(8-hydroxyquinoline)-aluminum (Alq3), Balq, Salq and Almq3; and hasa thickness of 10 nm˜100 nm.
 8. The electroluminescence device accordingto claim 3, wherein the electron blocking layer, the hole blocking layeror the electron/hole blocking layer is formed of a material selectedfrom the group consisting of3-phenyl-4-(1-naphthyl)-5-phenyl-1,2,4-triazole (TAZ),2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), phenanthrolines,imidazoles, triazoles, oxadiazoles, and aluminum complexes; and has athickness of 5 nm˜50 nm.
 9. A method for fabricating anelectroluminescence device, comprising the steps of: patterning ahole-injecting anode on a substrate and forming a polymer hole transportlayer thereon; coating a nanocrystal dispersion on the polymer holetransport layer to form a nanocrystal light-emitting layer; forming anorganic electron transport layer on the nanocrystal light-emittinglayer; and forming an electron-injecting cathode on the organic electrontransport layer.
 10. The method according to claim 9, wherein thenanocrystal light-emitting layer is formed by dispersing nanocrystalssurface-bound by a photosensitive compound in a solvent which does notdamage the polymer hole transport layer to obtain a nanocrystaldispersion, and coating the nanocrystal dispersion on the polymer holetransport layer; or dispersing nanocrystals surface-bound by a materialcontaining no photosensitive functional group and a photosensitivecompound in a solvent which does not damage the polymer hole transportlayer to obtain a nanocrystal dispersion, and coating the nanocrystaldispersion on the polymer hole transport layer.
 11. The method accordingto claim 9, wherein the nanocrystal light-emitting layer is made of atleast one material selected from the group consisting of metalnanocrystals, Group II-VI compound semiconductor nanocrystals, GroupIII-V compound semiconductor nanocrystals, PbS, PbSe and PbTe, the metalnanocrystals including Au, Ag, Pt, Pd, Co, Cu and Mo, the Group II-IVcompound semiconductor nanocrystals including CdS, CdSe, CdTe, ZnS,ZnSe, ZnTe, HgS, HgSe and HgTe, the Group III-V compound semiconductornanocrystals including GaN, GaP, GaAs, InP and InAs; and when thenanocrystal light-emitting layer is made of a mixture of two or morenanocrystals, the nanocrystals exist in the state of a simple mixture,fused crystals in which the nanocrystals are partially present in thesame crystal structure, or an alloy.
 12. The method according to claim10, wherein the solvent which does not damage the hole transport layerand disperses the nanocrystals is selected from the group consisting ofwater, pyridine, ethanol, propanol, butanol, pentanol, hexanol, toluene,chloroform, chlorobenzene, THF, cyclohexane, cyclohexene, methylenechloride, pentane, hexane, heptane, octane, nonane, decane, undecane,dodecane, and mixtures thereof.
 13. The method according to claim 9,wherein the electron transport layer is formed by spin coating, dipcoating, spray coating, or blade coating.
 14. The method according toclaim 10, wherein the nanocrystal dispersion has a concentration of 0.01wt %˜10 wt %.
 15. The method according to claim 9, wherein thenanocrystal light-emitting layer has a thickness of 3 nm˜30 nm.
 16. Themethod according to claim 9, wherein the polymer hole transport layer ismade of a material selected from the group consisting ofpoly(3,4-ethylenedioxythiophene) (PEDOT)/polystyrene para-sulfonate(PSS), poly-N-vinylcarbazole derivatives, polyphenylenevinylenederivatives, polyparaphenylene derivatives, polymethacrylatederivatives, poly(9,9-octylfluorene) derivatives, andpoly(spiro-fluorene) derivatives.
 17. The method according to claim 9,wherein the electron transport layer is formed on the nanocrystallight-emitting layer by thermal deposition, molecular deposition orchemical deposition.
 18. The method according to claim 9, furthercomprising the step of exposing the nanocrystal light-emitting layer toUV light to crosslink it, prior to coating the organic electrontransporting material on the nanocrystal light-emitting layer.
 19. Themethod according to claim 10, wherein the photosensitive compoundsurface-bound to the nanocrystals contains a double bond, a carboxylgroup, an amide group, a phenyl group, a biphenyl group, a peroxidegroup, an amine group, or an acryl group.
 20. The method according toclaim 9, further comprising the step of inserting a hole injection layerbetween the anode and the hole transport layer; inserting an electronblocking layer between the nanocrystal light-emitting layer and the holetransport layer; or inserting a hole blocking layer between thenanocrystal light-emitting layer and the electron transport layer.